This invention relates to novel compositions of matter which are highly effective as catalyst components, and to the preparation and use of such compositions.
Partially hydrolyzed aluminum alkyl compounds known as aluminoxanes (a.k.a. alumoxanes) are effective in activating metallocenes for polymerization ofolefins. Activating effects of water in such systems were initially noted by Reichert, et al. (1973) and Breslow, et al. (1975), and extended to trimethylaluminum-based systems by Sinn, Kaminsky, et al. (1976). Subsequent research by Sinn and Kaminsky demonstrated that this activation was due to formation of methylaluminoxane from partial hydrolysis of trimethylaluminum present in the system. Methylaluminoxane (a.k.a. methylalumoxane) has become the aluminum co-catalyst of choice in the industry.
Subsequent to the above original discoveries in this field, considerable worldwide effort has been devoted to improving the effectiveness of catalyst systems based on use of aluminoxanes or modified aluminoxanes for polymerization of olefins and related unsaturated monomers.
Representative of many patents in the field of aluminoxane usage in forming olefin polymerization catalyst systems with suitable metal compounds is U.S. Pat. No. 5,324,800 to Welborn et al. which claims an original filing date in 1983. This patent describes olefin polymerization catalysts made from metallocenes of a metal of Groups 4b, 5b, or 6b, and a cyclic or linear C1-C5 alkylaluminoxane. The cyclic and the linear aluminoxanes are depicted, respectively, by the formulas (Rxe2x80x94Alxe2x80x94O)n and R(Rxe2x80x94Alxe2x80x94O)nAIR2 where n is from 1 to about 20, and R is most preferably methyl. The aluminoxanes are made by controlled hydrolysis of the corresponding aluminum trialkyl.
Another relatively early patent in the field, U.S. Pat. No. 4,752,597 to Turner based on a filing date of 1985, describes olefin polymerization catalysts comprising the reaction products of a metallocene complex of group IVB, VB, VIB, and VIII of the periodic table and an excess of aluminoxane. These catalysts are formed by pre-reacting a metallocene and an aluminoxane in mole ratios greater than 12:1, such as about 12:1 to about 100:1, to produce a solid product which precipitates from solution. Despite assertions of suitable catalytic activity, in reality the activity of these materials is so low as to be of no practical importance whatsoever.
In U.S. Pat. Nos. 4,960,878 and 5,041,584 to Crapo et al. modified methyl-aluminoxane is formed in several ways. One involves reacting a tetraalkyldialuminoxane, R2Alxe2x80x94Oxe2x80x94AIR2, containing C2 or higher alkyl groups with trimethylaluminum (TMA) at xe2x88x9210 to 150xc2x0 C. Another involves reacting TMA with a polyalkylaluminoxane (xe2x80x94Al(R)xe2x80x94Oxe2x80x94)n where R is C2 alkyl or higher and n is greater than 1, e.g., up to 50. Temperatures suggested for this reaction are xe2x88x9220 to 50xc2x0 C. A third way involves conducting the latter reaction and then reacting the resultant product, which is indicated to be a complex between trimethylaluminum and the polyalkylaluminoxane, with water. The patent states that the water-to-aluminum ratios used to make the polyalkylaluminoxane reagent have an effect on the activity of the final methylaluminoxane. On the basis of ethylene polymerizations using zirconocene dichloride catalyst and a complex of trimethylaluminum with polyisobutylaluminoxane subsequently reacted with water (MMAO) as co-catalyst, it is indicated in the patent that the highest polymerization activities were achieved with MMAO co-catalyst prepared at H2O/Al ratios of about 0.6 to about 1.0 and Al/Zr ratios in the range of 10,000/1 to 400,000/1.
Various references are available indicating that isobutylaluminoxanes themselves are relatively ineffective on their own as co-catalysts. For example, several other reactions of alkylaluminum compounds with water are disclosed in U.S. Pat. Nos. 4,960,878 and 5,041,584. Thus in Example 1 of these patents, DIBAL-O (tetraisobutyldialuminoxane), a commercial product, was prepared by reaction of water with triisobutylaluminum (TIBA) in heptane using a water/TIBA ratio of about 0.5, followed by solvent stripping at 58-65xc2x0 C. under vacuum. In Examples 3-6 of the patents isobutylaluminoxane (IBAO) was prepared by controlled addition of water to a 25% solution of TIBA in toluene in the temperature range of 0-12xc2x0 C., followed by heating to 70-80xc2x0 C. to ensure complete reaction and remove dissolved isobutane. H2O/Al ratios used were 0.98, 1.21, 1.14, and 0.88. IBAO was again made in a similar manner in Example 52 of the patents. Here the H2O/Al ratio was 0.70, and the product was heated at 75xc2x0 C. And in Example 70 tri-n-butylaluminum (TNBA) in toluene was treated at 0-10xc2x0 C. with water followed by heating to 85xc2x0 C. Ethylene polymerizations using zirconocene dichloride catalyst and various products from the foregoing Examples were conducted. Specific activities (xc3x97103 gPE/(gZr.atm C2H4.hr)) of the catalysts made with DIBAL-O from Ex. 1, IBAO from Ex. 3, and IBAO from Ex. 6 were, respectively, 4.1, 4.2, and 7.7, as compared to 1000 for the catalyst made using conventional MAO as the co-catalyst. The patents acknowledge that tetraisobutyldialuminoxane (DIBAL-O) showed xe2x80x9cpoor polymerization activityxe2x80x9d, and from the foregoing test results the same can be said to apply to IBAO.
WO 96102580 to Dall""occo, et al. describes olefin polymerization catalysts made by contacting a metallocene of Ti, Zr, or Hf, an organoaluminum compound having at least one specified hydrocarbon substituent on the xcex2-carbon atom of an aliphatic group bonded to an aluminum atom, and water. Various ways of bringing these components together are suggested. Polymerizations described were carried out using Al/Zr mole ratios ranging from 500 up to as high as 5000.
EP 0 277 004 to Turner, published in 1988, describes the successful preparation and use as catalysts composed of an ionic pair derived from certain metallocenes of Group 4, mostpreferably bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl, reacted with certain trisubstituted ammonium salts of a substituted or unsubstituted aromatic boron compound, most preferably N,N-dimethylanilinium tetra(pentafluorophenyl)boron. While EP 0 277 004 mentions that compounds containing an element of Groups V-B, VI-B, VII-B, VIII, I-B, II-B, 111-A, IV-A, and V-A may be used in forming the catalysts, no specific compounds other than boron compounds are identified. In fact, EP 0 277 004 appears to acknowledge inability to identify specific compounds other than boron compounds by stating: xe2x80x9cSimilar lists of suitable compounds containing other metals and metalloids which are useful as second components could be made, but such lists are not deemed necessary to a complete disclosure.xe2x80x9d See in this connection Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.
U.S. Pat. No.5,153,157 to Hlatky and Turner states that its process xe2x80x9cis practiced with that class of ionic catalysts referred to, disclosed, and described in European Patent Applications 277,003 and 277,004.xe2x80x9d The process of U.S. Pat. No.5,153,157 involves forming an ionic catalyst system from two components. The first is a bis(cyclopentadienyl) derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second component or portion thereof such as a cation portion thereof The second component is referred to as an ion exchange compound comprising (1) a cation which will irreversibly react with a ligand of the Group IV-B metal compound and (2) a noncoordinating anion which is bulky, labile, and stable. The second component, also termed an activator component, comprises compounds of Groups V-B, VI-B, VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A identified by a general formula. Besides referring to the boron compounds of EP 277,004, supra, such as tri(n-butylammonium)tetra(pentafluorophenyl)boron and N,N-dimethylanilinium tetra(pentafluorophenyl)boron as suitable activators, the U.S. ""157 patent teaches use of boron compounds having a plurality of boron atoms, and also trialkyl aluminum compounds, triaryl aluminum compounds, dialkylaluminum alkoxides, diarylaluminum alkoxides, and analogous compounds of boron. Of the organoaluminum activators triethylaluminum and trimethylaluminum are specified as most preferred. The Examples show use of a catalyst system formed from (1) a solution of bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl and N,N-dimethylanilinium tetra(pentafluorophenyl)boron together with (2) triethylborane, triethylaluminum, tri-sec-butylborane, trimethylaluminum, and diethylaluminum ethoxide. In some cases the catalyst formed from the metallocene and the N,N-dimethylanilinium tetra(pentafluorophenyl)boron without use of a compound of (2) gave no polymer at all under the polymerization conditions used.
U.S. Pat. No.5,198,401 to Turner, Hlatky, and Eckman refers, in part, to forming catalyst compositions derived from certain metallocenes of Group 4, such as bis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafnium dimethyl, reacted with certain trisubstituted ammonium salts of a substituted or unsubstituted aromatic boron compound, such as N,N-dimethylanilinium tetra(pentafluorophenyl)boron or tributylammonium tetra(pentafluorophenyl)boron as in EP 0 277 004. However here the anion is described as being any stable and bulky anionic complex having the following molecular attributes: 1) the anion should have a molecular diameter about or greater than 4 angstroms; 2) the anion should form stable salts with reducible Lewis acids and protonated Lewis bases; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing or oxidizing agent. Anions of this type are identified as polynuclear boranes, carboranes, metallacarboranes, polyoxoanions and anionic coordination complexes. Elsewhere in the patent it is indicated that any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Bronsted or Lewis acids) may be used or contained in the second activator compound [the first activator compound appears not to be disclosed]. Suitable metals of the second activator compound are stated to include, but not be limited to, aluminum, gold, platinum and the like. No such compound is identified. Again after listing boron compounds the statement is made that xe2x80x9cSimilar lists of suitable compounds containing other metals and metalloids which are useful as second components could be made, but such lists are not deemed necessary to a complete disclosure.xe2x80x9d In this connection, again note Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.
Despite the above and many other efforts involving aluminum co-catalysts, the fact remains that in order to achieve suitable catalysis on a commercial basis, relatively high aluminum to transition metal ratios must be employed. Typically for optimal activity an aluminum to metallocene ratio of greater than about 1000:1 is required for effective homogeneous olefin polymerization. According to Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34 1143-1170:
xe2x80x9cCatalytic activities are found to decline dramatically for MAO concentrations below Al:Zr ratio roughly 200-300:1. Even at Al:Zr ratios greater than 1000:1 steady state activities increase with rising MAO concentrations approximately as the cube root of the MAO concentrationxe2x80x9d.
This requirement of high aluminum loading is mainly caused by a metallocene activation mechanism in which generation of catalytically active species is equilibrium driven. In this role MAO acts as a Lewis acid to remove by group transfer a leaving group X{circle around (xe2x88x92)} from the transition metal. This forms a weakly-coordinating anion, MAO-X{circle around (xe2x88x92)}, in the corresponding transition metal cation. That is, in such systems the following equilibrium exists: 
The Lewis acid sites in MAO abstract a negatively charged leaving group such as a methide group from the metallocene to form the catalytically active ion pair. The activation process is reversible and Keq is typically small. Thus the ion pair can return to its neutral precursors which are catalytically inactive. To overcome this effect, a large excess of MAO is required to drive the equilibrium to the right.
The high aluminum loadings required for effective catalysis in such systems result in the presence of significant levels of aluminum-containing residues (xe2x80x9cashxe2x80x9d) in the polymer. This can impair the clarity of finished polymers formed from such catalyst systems.
A further disadvantage of MAO is its limited solubility in paraffinic hydrocarbon solvents. Polymer manufacturers would find it of considerable advantage to have in hand aluminoxane and metallocene-based materials having high paraffin solubility.
Still another disadvantage of MAO has been its relatively high cost. For example, in an article entitled xe2x80x9cEconomics is Key to Adoption of Metallocene Catalystsxe2x80x9d in the Sep. 11, 1995 issue of Chemical and Engineering News, Brockmeier of Argonne National Laboratory concluded that xe2x80x9ca reduction in costs or amount of MAO has the potential for greatly reducing the costs to employ metallocene catalystsxe2x80x9d.
Thus it would be of inestimable value to the art if a way could be found of providing catalyst components based on use of aluminoxanes that are effective co-catalysts for use with transition metal compounds at much lower aluminum:metal ratios than have been effective heretofore. In addition, the art would be greatly advanced if this could be accomplished with aluminoxane compositions that are less expensive than MAO, that have high solubility in paraffinic solvents and that produce lower ash residues in the polymers.
The invention described and claimed in the Parent Application is deemed to have fulfilled most, if not all, of the foregoing desirable objectives. In brief summary, that invention makes it possible to provide catalyst compositions in which a low cost co-catalyst can be employed at very low Al loadings. Such catalyst compositions typically have high solubility in paraffinic solvents. Moreover they yield reduced levels of ash and result in improved clarity in polymers formed from such catalyst compositions. Making all of this possible is the provision of a compound which comprises (i) a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group, and (ii) an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group. In contrast to aluminoxanes used prior to the Parent Application and acting as Lewis acids (Eq. 1), the present compositions utilize hydroxyaluminoxane species (HOxe2x80x94AO) acting as Brxc3x8nsted acids. In the formation of such compounds, a cation is derived from the transition, lanthanide or actinide metal compound by loss of a leaving group, and this cation forms an ion pair with an aluminoxate anion devoid of such leaving group. The leaving group is typically transformed into a neutral hydrocarbon thus rendering the catalyst-forming reaction irreversible as shown in Equation 2:
Cp2MXR+HOxe2x80x94AOxe2x86x92[Cp2Mxe2x80x94X]⊕(Oxe2x80x94AO){circle around (xe2x88x92)}+RHxe2x80x83xe2x80x83(Eq. 2)
Note the absence of the leaving group, X, in the anion OAO{circle around (xe2x88x92)} as compared to the presence of X in the anion, (X-MAO){circle around (xe2x88x92)}, of Equation 1.
In many of the patents related to the use of aluminoxanes as metallocene co-catalysts, rather broad and generalized assertions have been routinely made regarding aluminum-to-metallocene ratio, types of alkyl aluminoxanes, and ratio of water to aluminum for forming aluminoxanes. However, there is no disclosure of any type that would suggest, let alone demonstrate, the use of an aluminoxane as a Brxc3x8sted acid to activate metallocenes and related organometallic catalysts. There are, furthermore, no known prior teachings or descriptions of how to use an aluminoxane as a Brxc3x8sted acid muchless that by so doing it would be possible to reduce the ratio of aluminum to transition, lanthanide or actinide metal to an unprecedentedly low level.
In another of its embodiments the invention of the Parent Application provides a process which comprises contacting a transition, lanthanide or actinide metal compound having at least two leaving groups with a hydroxyaluminoxane in which at least one aluminum atom has a hydroxyl group bonded thereto so that one of said leaving groups is lost. As noted above, during the formation of such compounds, an aluminoxate anion is formed that is devoid of the leaving group. Instead the leaving group is typically transformed into a neutral hydrocarbon so that the catalyst forming reaction is irreversible.
Still another embodiment of the invention of the Parent Application is a process of polymerizing at least one polyrierizable unsaturated monomer, which process comprises contacting said monomer under polymerization conditions with a compound which comprises a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group.
Other embodiments of the invention of the Parent Application include catalyst compositions in which a compound comprising a cation derived from a transition, lanthanide or actinide metal compound, preferably a metallocene, by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group is supported on a carrier.
It has now been found that, surprisingly, the catalyst compositions as described in the Parent Application and also herein can have exceptional stability once recovered and maintained under suitable conditions in the absence of a solvent. In fact, it has been found possible to store a solid catalyst of this type in a drybox at ambient room temperatures for a one-month period without loss of its catalytic activity. In contrast, the same catalyst composition is relatively unstable if left in the reaction solution or put in solution after it has been removed from solution.
This invention thus makes it possible, apparently for the first time ever, to prepare an active olefin polymerization catalyst that is sufficiently stable in unsupported form to be placed in storage and shipped for use long after it has been prepared. So far as is known, it has not been possible heretofore to do this with unsupported catalysts. Only with certain active olefin polymerization catalysts on catalyst supports has this been accomplished previously.
Because the present active catalysts are more stable in their undissolved state than when they are in solution, it is now possible to prepare both unsupported and supported olefin polymerization catalyst compositions that can be stored and shipped in undissolved form. The present catalyst compositions are typically kept in an atmosphere of dry inert gas or in a vacuum after the catalyst has been formed and recovered, and optionally, subjected to one or more finishing procedures. By xe2x80x9cfinishing procedurexe2x80x9d is meant any procedure or operation which neither significantly changes the chemical composition of the catalyst nor excessively diminishes the catalytic activity of the catalyst to such an extent that it is no longer of practical utility as a catalyst, which procedure or operation involves having the catalyst in solution or slurry form in order to conduct the procedure or operation and that is conducted at any time after such catalyst has been formed and recovered from the medium in which it was formed, excluding of course, the use of the catalyst in a polymerization reaction. Finishing procedures thus can include such procedures or operations as purifying the catalyst, improving the appearance of the catalyst, converting the catalyst into a supported catalyst, and the like. For example, after its formation and recovery (isolation) from the medium in which it was formed, the catalyst can be purified and/or cosmetically improved by dissolving the catalyst in, and crystallizing or precipitating the catalyst from, a suitable solvent followed by drying, or washing the catalyst with a suitable anhydrous inert solvent followed by drying, all under an inert anhydrous atmosphere, and/or by use of some other purification procedure(s) and/or appearance-improving procedure(s) that involve having the catalyst in solution or slurry form during all or a portion of the procedure(s), and that do not significantly change the chemical composition or excessively diminish the catalytic activity of the catalyst so that it is no longer useful as a catalyst for polymerization of, say, ethylene or propylene. Another example of a finishing procedure is the preparation of a supported catalyst, such as by depositing the catalyst on a catalyst support material from a solution of the catalyst. It will of course be understood that during a finishing procedure the catalyst should be not be exposed to water or any other substance or condition that will materially destroy its catalytic activity or materially change its chemical composition.
Some finishing procedure(s) would be conducted before storing the purified compound in a dry inert environment such as in an anhydrous inert atmosphere or under vacuum. However the optional finishing procedure can be performed whenever it is appropriate to do so. Thus it is within the scope of this invention to carry out any finishing procedure at any time after the catalyst has been formed and recovered from the medium in which it was formed. As noted above, use of the catalyst as a catalyst or catalytic component does not come within the meaning of a finishing procedure.
After preparation and recovery, the present catalysts can be mixed in the absence of a solvent and under suitable inert anhydrous conditions with an another substance that is inert or sufficiently inert to the catalyst as to enable the formation of an undissolved mixture which can be stored and shipped in much the same way as the same catalyst in isolated condition. In other words, neither the catalyst nor the other substance is dissolved in whole or in part in an ancillary solvent in forming such mixture. A few illustrative examples of substances which can be mixed with the catalyst, such as by dry blending under suitable inert anhydrous conditions, are (i) particulate or powdery dry, anhydrous silica, alumina, or silica-alumina; (ii) dry particles of a polyolefin polymer; or (iii) any other dry material which is inert to the catalyst and which does not dissolve (solvate) the catalyst, e.g., dry glass beads, chopped glass fiber, inert metal whiskers, dry carbon fibers, or the like.
Except when being subjected to an optional finishing procedure or optional mixing procedure with one or more inert substances, the catalyst composition, whether in isolated form, in the form of a solvent-free mixture with one or more inert substances, or supported on a catalyst support, is stored or transported or otherwise handled under or in a dry, anhydrous environment or atmosphere. The term xe2x80x9cisolatedxe2x80x9d is being used herein to denote that no other substance is intentionally mixed with or placed in contact with the catalytic composition except for an inert atmosphere (or vacuum) and a suitable container.
In the practice of this invention the stable isolated catalyst compositions, the stable supported catalyst compositions, and the solvent-free mixtures of catalyst composition and inert substance(s) can be stored and transported by the manufacturer, and stored by the consumer, all without need for refrigeration, and then used as an active preformed catalyst in the polymerization of polymerizable olefinic compounds. Thus the operations of both the catalyst manufacturer and the consumer, when different parties, can both be greatly simplified. This can be accomplished pursuant to this invention by maintaining (i) the isolated catalyst composition, (ii) an undissolved mixture of the catalyst composition with one or more other inert materials that do not dissolve the catalyst composition, or (iii) a supported catalyst composition of this invention, in a dry inert atmosphere from the time of the removal or separation of the catalyst composition from solution to the time of its use. It will be understood and appreciated, however, that one exposure of the catalyst composition to a small amount of moisture and/or air or more than one exposure of the catalyst composition to a small total amount of moisture and/or air, which amount or total amount does not destroy substantially an entire quantity of the isolated catalyst composition, can be tolerated and thus is not excluded from the scope of this invention. But of course, one should try to minimize the extent of such exposure(s) as much as is practicable under any given set of circumstances. This is simply a matter of common sense. Where one or more such exposures, inadvertent or otherwise, has occurred, and there is a possibility that the entire quantity of the catalyst has not been harmed, a representative sample of such previously-exposed catalyst should be tested for catalytic activity. If the test indicates that the previously-exposed catalyst remains sufficiently catalytically active, it would seem reasonable to keep the remainder of the previously-exposed catalyst under proper storage conditions for future use. On the other hand, if the test indicates that the previously-exposed catalyst no longer possesses sufficient catalytic activity, then it would seem reasonable to discard the remainder of the previously-exposed catalyst.
Accordingly, this invention utilizes all of the new compounds and all of the new processes of the Parent Application. The added features of this invention are to recover the catalyst composition (catalytic compound) after its preparation, optionally subject the catalyst composition to one or more finishing procedures and/or optionally mix the catalyst composition with one or more inert substances under suitable inert anhydrous conditions, and store the catalyst composition by itself, in supported form or as a solvent-free mixture with one or more inert substances under suitable conditions which minimize exposure to moisture and air (oxygen) as much as reasonably possible.
Thus in one of its embodiments this invention provides a compound which comprises a cation derived from d-block or f-block metal compound by loss of a leaving group and an aluminoxate anion derived by transfer of a proton from a stable or metastable hydroxyaluminoxane to said leaving group, wherein such compound is in undissolved form in a dry, inert atmosphere or environment. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
Another embodiment of this invention is a compound which comprises a cation derived from a d-block or f-block metal compound by loss of a leaving group and an aluminoxate anion devoid of said leaving group, wherein the compound comprised of such cation and aluminoxate anion is in undissolved form in a dry, inert atmosphere or environment. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
A further embodiment is a compound which comprises a cation derived from a d-block or f-block metal compound by loss of a leaving group transformed into a neutral hydrocarbon, and an aluminoxate anion derived by loss of a proton from a hydroxyaluminoxane having, prior to said loss, at least one aluminum atom having a hydroxyl group bonded thereto, wherein the compound comprised of such cation and aluminoxate anion is in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed. In addition, the compound is kept in a dry, inert atmosphere during a storage period. Preferably the compound in such atmosphere or environment is in isolated form or is in supported form on a catalyst support.
The compounds of each of the above embodiments of this invention can be used as a catalyst either in the solid state or in solution. The stability of the compound when in solution is sufficient to enable the compound to perform as a homogeneous catalyst.
Still another embodiment of this invention is a process which comprises contacting a d-block or f-block metal compound having at least two leaving groups with a hydroxyaluminoxane in which at least one aluminum atom has a hydroxyl group bonded thereto so that one of said leaving groups is lost; recovering the resultant metal-containing compound so formed; and storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment. Such compound is maintained in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
Also provided as another embodiment of this invention is a process which comprises donating a proton from an aluminoxane to a leaving group of a d-block or f-block metal compound to form a compound composed of a cation derived from said metal compound and an aluminoxate anion devoid of said leaving group; recovering the compound composed of such cation and aluminoxate anion; storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment; and maintaining such compound in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
Another embodiment is a process which comprises interacting a d-block or f-block metal compound having two leaving groups and a hydroxyaluminoxane having at least one aluminum atom that has a hydroxyl group bonded thereto to form a compound composed of a cation through loss of a leaving group which is transformed into a neutral hydrocarbon, and an aluminoxate anion derived by loss of a proton from said hydroxyaluminoxane; recovering the compound composed of such cation and aluminoxate anion; storing such recovered compound (preferably in isolated form or in supported form on a catalyst support) in an anhydrous, inert atmosphere or environment; and maintaining such compound in undissolved form except during one or more optional finishing procedures, if and when any such finishing procedure is performed.
The above and other embodiments, features, and advantages of this invention will become still further apparent from the ensuing description and appended claims.